Herbicidal 3-hydroxy-2-cyclohexen-1-ones

ABSTRACT

Herbicidal 3-hydroxy-2-cyclohexen-1-ones of the formula ##STR1## wherein R 1  and R 2  each is hydrogen or methyl, 
     R 3  is C 1-4  alkyl, cyclopropylmethyl, C 3-4  alkenyl which may be substituted by one to three halogen atoms or C 3-4  alkynyl, 
     R 4  is C 1-4  alkyl, 
     R 5  each independently is halogen, C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy, C 1-4  haloalkoxy, C 1-4  alkylthio, C 1-4  haloalkylthio or cyano, 
     n is 0, 1 or 2, and 
     m is 0, 1 or 2.

The present invention relates to novel 3-hydroxy-2-cyclohexen-1-ones, toprocesses for their preparation and to their use as herbicides.

It has already been disclosed that a certain group of cyclohexanederivatives has herbicidal activities. (see Japanese Patent Laid-openNos. 115,349/1979, 146,856/1988 and 13066/1989)

There have now been found novel 3-hydroxy-2-cyclohexen-1-ones of theformula (I) ##STR2## wherein

R¹ and R² each is hydrogen or methyl,

R³ is C₁₋₄ alkyl, cyclopropylmethyl,

C₃₋₄ alkenyl which may be substituted by one to three halogen atoms orC₃₋₄ alkynyl,

R⁴ is C₁₋₄ alkyl,

R⁵ each independently is halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl C₁₋₄alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, C₁₋₄ haloalkylthio or cyano,

n is 0, 1 or 2, and

m is 0, 1 or 2.

The compounds of the formula (I) can be obtained by a process in which,

a) where n is 0;

compounds of the formula (II) ##STR3## wherein R¹, R², R⁴, R⁵ and m havethe same meanings as mentioned above, are reacted with compounds of theformula (III)

    R.sup.3 --O--NH.sub.2                                      (III)

wherein R³ has the same meaning as mentioned above, or a salt of thecompounds of the formula (III), in the presence of inert solvents, andif appropriate, in the presence of an acid binder, and

b) where n is 1 or 2;

compounds of the formula (Ia) ##STR4## wherein R¹, R², R³, R⁴, R⁵ and mhave the same meanings as mentioned before, are reacted with anoxidizing agent in the presence of inert solvents.

The novel 3-hydroxy-2-cyclohexen-1-ones exhibit powerful herbicidalproperties.

Surprisingly, the compounds of the formula (I) according to theinvention exhibit not only a substantially greater herbicidal actionthan those known from the aforesaid prior art, but also favorablecompatibility with crops.

In the formula (I) of the compounds according to the present invention,preferably R¹ and R² each represent hydrogen or methyl,

R³ represents C₁₋₄ alkyl or C₃₋₄ alkenyl that may be substituted by oneto three halogen atoms,

R⁴ represents C₁₋₃ alkyl,

R⁵ represents chlorine, fluorine or trifluoromethyl,

n is 0, 1 or 2, and

m is 0, 1 or 2 wherein when m is 2, R⁵ may be the same or different.

Further, in the formula (I), most preferably,

R¹ and R² each represent hydrogen,

R³ represents ethyl or allyl, by chlorine,

R⁴ represents methyl or ethyl,

R⁵ represents chlorine, fluorine or trifluoromethyl,

n is 0, and

m is 0 or 1.

Specifically, the following compounds may be mentioned:

5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-one;

5-[2-(3-chlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-one;

5-[2-(3-chloro-4-fluorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-one;

5-{2-[3-chloro-4-(trifluoromethyl)phenylthio]ethyl}-3-hydroxy-2-(1-ethoxyimino)-ethyl-2-cyclohexen-1-one;

5-[2-(3-chloro-2-methylphenylthio)ethyl]-3-hydroxy-2-(1-allyloxyimino)propyl-2-cyclohexen-1-one;

5-[2-(3-chloro-4-fluorophenylthio)ethyl]-3-hydroxy-2-(1-allyloximino)propyl-2-cyclohexen-1-one;

5-[2-(2-methyl-3-chlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-one.

If, for example, in the above process a),5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-propionyl-2-cyclohexen-1-oneand O-methylhydroxylamine hydrochloride are used as the startingmaterials, the reaction can be represented as follows: ##STR5##

If, for example, in the above process b),5-[2-(3,5-dichlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-oneand meta-chloro perbenzoic acid are used as the starting materials, forexample, the reaction can be represented as follows: ##STR6##

The compounds of the formula (II) include novel compounds that can beprepared by rearranging compounds of the formula (IV) ##STR7## whereinR¹, R², R⁴, R⁵ and m have the same meanings as mentioned before.

The above compounds of the formula (IV) can be prepared by reactingcompounds of the formula (V) ##STR8## wherein R¹, R², R⁵ and m have thesame meanings as mentioned before, with compounds of the formula (VI)##STR9## wherein R⁴ has the same meaning as mentioned before and Halmeans a halogen atom.

The compounds of the formula (V) can be prepared by a process disclosedin Japanese Patent Laid-open No. 13066/1989.

The compounds of the formula (VI) are well known in organic chemistryand as an example, there may be mentioned propionyl chloride.

The compounds represented by the general formula (III) are well known inorganic chemistry and, as examples, there may be mentioned the following

O-methylhydroxylamine, O-ethylhydroxylamine and O-allylhydroxylamine,and hydrochlorides thereof.

In the above process b), the compounds of the formula (Ia) can beprepared by the above process a) and said compounds are a part of thecompounds of the formula (I).

As examples thereof, there may be mentioned:

5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-oneand

5-[2-(3-chloro-4-methylthiophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-one.

As the oxidizing agent used in the above process b), use may be made,for example, of organic peroxides such as meta-chloroperbenzoic acid,hydrogen peroxide and the like.

In carrying out the process a) mentioned above, use may be made, assuitable diluent, of any inert solvent.

Examples of such diluents are water; aliphatic, cycloaliphatic andaromatic, optionally chlorinated, hydrocarbons such as hexane,cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene,methylene chloride, chloroform, carbon tetrachloride, ethylene chloride,1,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; etherssuch as diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutylether, dioxane, tetrahydrofuran and the like; nitriles such asacetonitrile, propionitrile, acrylonitrile and the like; alcohols suchas methanol, ethanol, iso-propanol, butanol, ethylene glycol, 2-methoxyethanol and the like, esters such as ethyl acetate, amyl acetate and thelike; acid amides such as dimethyl formamide, N,N-dimethylacetamide andthe like and sulfones and sulfoxides such as dimethylsulfoxide,sulfolane and the like; and bases, for example, such as pyridine.

The above-mentioned process a) is carried out preferably in the presenceof an acid binder and, as the acid binder, there may be mentioned, forexample, the hydroxide, carbonate, bicarbonate and alcoholate of alkalimetals, tertiary amines such as, for example, triethylamine,tributylamine, 1,1,4,4-tetramethylethylenediamine, N,N-dimethylaniline,N,N-diethylaniline, pyridine, 4-dimethylamino pyridine (DMAP),1,4-diazabicyclo[2,2,2]octane (DABCO), and1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

In the above-mentioned process a), the reaction temperature can bevaried within a substantially wide range. In general, the reaction iscarried out at a temperature of from about 0° C. to 100° C., preferablyat room temperature.

Further, the reaction is carried out under normal pressure, although itis also possible to employ a higher or reduced pressure.

When the above-mentioned process a) according to the present inventionis carried out, use is made, for example, of about once or twice molesof the compounds of the formula (III) per mole of the compounds of theformula (II) in the presence of 1.0 to 2.0 triethylamine dissolved in aninert solvent such as methanol, for example, to obtain the desiredcompound.

When use is made, in carrying out the process b) mentioned above, oforganic peroxides as oxidizing agent, the following solvents may be usedas suitable diluents:

aliphatic, cycloaliphatic and aromatic, optionally chlorinated,hydrocarbons such as hexane, cyclohexane, petroleum ether, ligroin,benzene, toluene, xylene, methylene chloride, chloroform, carbontetrachloride, ethylene chloride, 1,2-dichloroethane, chlorobenzene,dichlorobenzene and the like; alcohols such as methanol, ethanol,iso-propanol, butanol, ethylene glycol, 2-methoxyethanol and the like;esters such as ethyl acetate, amyl acetate; and acid amides such asdimethyl formamide, dimethyl acetamide and the like.

When use is made, in carrying out the above-mentioned process b), ofhydrogen peroxide as oxidizing agent, the following solvents may be usedas suitable solvents:

water that may be basic, neutral or acidic; alcohols such as, forexample, methanol, ethanol, iso-propanol, butanol, ethyleneglycol,2-methoxyethanol; carboxylic acids such as acetic acid for example.

In the above-mentioned process b), the reaction temperature can bevaried within a substantially wide range. When n is 1 in formula (I),the reaction is carried out, in general, at a temperature of from about0° C. to about 25° C., preferably from about 0° C. to about 10° C. Whenn is 2, the temperature may be from about 50° C. to about 100° C.,preferably from about 80° C. to about 100° C.

The reaction is preferably carried out under normal pressure, althoughit is also possible to employ a higher or reduced pressure.

When the above-mentioned process b) according to the present inventionis carried out, use is made, for example, of about 1.0 to 2.4 moles ofmeta-chloroperbenzoic acid per mole of the compounds of the formula (Ia)in the presence of an inert solvent such as, for example, methanol toobtain the desired compound.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weedkillers. By weed, in the broadest sense, there are tobe understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the selective combating of weeds in annual cultures.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,foams, pastes, granules, aerosols, natural and synthetic materialsimpregnated with active compound, very fine capsules in polymericsubstances, coating compositions for use on seed, and formulations usedwith burning equipment, such as fumigating cartridges, fumigating cansand fumigating coils, as well as ULV cold mist and warm mistformulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 percent by weight ofactive compound, preferably from 0.5 to 90 percent by weight.

The active compounds according to the invention, as such or in the formof their formulations, can also be used, for combating weeds, asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Possible components for the mixtures are known herbicides, such as, forexample,4-amino-6-(1,1-dimethylethyl)-3-ethylthio-1,2,4-triazin-5(4H)-one,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dioneor N-(2-benzothiazolyl)-N,N'-dimethyl-urea, for combating weeds incereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one for combatingweeds in sugar beets and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one forcombating weeds in soy beans. Surprisingly, some mixtures also show asynergistic action.

Mixtures with other known active compounds, such as herbicides,fungicides, insecticides, acaricides, nematicides, bird repellents,plant nutrients and agents which improve soil structure, are alsopossible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing. They areused, in particular, after emergence of the plants.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between about 0.04 and 4 kg of active compound perhectare of soil surface, preferably between about 0.05 and 2 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATIVE EXAMPLES EXAMPLE 1 ##STR10##

To a solution of5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-propionyl-2-cyclohexen-1-one(0.75 g) and triethylamine (0.4 g) dissolved in methanol (15 ml) wasadded O-methylhydroxylamine hydrochloride (0.02 g) and the mixturesolution was agitated at room temperature for 12 hours. After thereaction of the mixture solution had been completed, the solvent wasdistilled off, followed by addition of dilute hydrochloric acid thereto.The reaction product was extracted with ethyl acetate three times and,after drying over anhydrous sodium sulfate, was freed from the solventby evaporation under reduced pressure. The thus obtained oily residuewas purified through silicagel column chromatography(hexane:ethylacetate=2:1) to give5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-(1-methoxyimino)propyl-2-cyclohexen-1-one(0.62 g). n_(D) ²⁰ 1.5909.

Together with the compound obtained in Example 1, Table 1 which followssets forth compounds which can be obtained by the same method as inExample 1:

                                      TABLE 1                                     __________________________________________________________________________     ##STR11##                                                                    Comp.                                                                         No. R.sup.1                                                                          R.sup.2                                                                          R.sup.3   R.sup.4                                                                              (R.sup.5).sub.m                                                                       n                                          __________________________________________________________________________    1   H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             --      0                                          2   H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.3                                                                             --      0 n.sub.D.sup.20 1.5904                    3   H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             --      0 n.sub.D.sup.20 1.5934                    4   H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             --      0 n.sub.D.sup.20 1.5883                    5   H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      --      0 n.sub.D.sup.20 1.5989                    6   H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      --      0 n.sub.D.sup.20 1.5967                    7   H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                      --      0 n.sub.D.sup.20 1.5802                    8   H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      --      0 n.sub.D.sup.20 1.5901                    9   H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      --      0 n.sub.D.sup.20 1.5807                    10  H  H  CH.sub.3  CH.sub.2 CH.sub.2 CH.sub.3                                                           --      0                                          11  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                           --      0 n.sub.D.sup.20 1.5792                    12  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.2 CH.sub.2 CH.sub.3                                                           --      0                                          13  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CH.sub.2 CH.sub.3                                                           --      0 n.sub.D.sup.20 1.5383                    14  H  H  CH.sub.2 CHCHCl                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                           --      0 n.sub.D.sup.20 1.5685                    15  H  H  CH.sub.2 CCH                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                           --      0                                          16  H  CH.sub.3                                                                         CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             5-Cl    0                                          17  H  CH.sub.3                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.3                                                                             5-Cl    0                                          18  H  CH.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             5-Cl    0                                          19  H  CH.sub.3                                                                         CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             5-Cl    0                                          20  H  CH.sub.3                                                                         CH.sub.3  C.sub.2 H.sub.5                                                                      5-Cl    0                                          21  H  CH.sub.3                                                                         CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5850                    22  H  CH.sub.3                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5951                    23  H  CH.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      5-Cl    0                                          24  H  CH.sub.3                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0                                          25  H  CH.sub.3                                                                         CH.sub.2 CCH                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0                                          26  H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      6-Cl    0 n.sub.D.sup.20 1.5576                    27  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      6-Cl    0 n.sub.D.sup.20 1.5736                    28  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                      6-Cl    0                                          29  H  H  CH.sub. 2 CHCH.sub.2                                                                    C.sub.2 H.sub.5                                                                      6-Cl    0                                          30  H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      6-Cl    0                                          31  H  H  CH.sub.2 CCH                                                                            C.sub.2 H.sub.5                                                                      6-Cl    0                                          32  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             5-Cl    0 Oily                                     33  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.3                                                                             5-Cl    0 n.sub.D.sup.20 1.5911                    34  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             5-Cl    0 n.sub.D.sup.30 1.5941                    35  H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             5-Cl    0                                          36  H  H  CH.sub.2 CCH                                                                            CH.sub.3                                                                             5-Cl    0                                          37  H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.6049                    38  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      5-Cl    0                                          39  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5806                    40  H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5923                    41  H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      5-Cl    0                                          42  H  H  CH.sub.2 CCH                                                                            C.sub.2 H.sub.5                                                                      5-Cl    0                                          43  H  H  CH.sub.3  CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 Oily                                     44  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 Oily                                     45  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 n.sub.D.sup.20 1.5803                    46  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 Oily                                     47  H  H  CH.sub.2 CHCHCl                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0                                          48  H  H  CH.sub.2 CCH                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0                                          49  CH.sub.3                                                                         H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             5-Cl    0                                          50  CH.sub.3                                                                         H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.3                                                                             5-Cl    0                                          51  CH.sub.3                                                                         H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 n.sub.D.sup.20 1.5799                    52  CH.sub.3                                                                         H  CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 n.sub.D.sup. 20 1.5850                   53  CH.sub.3                                                                         H  CH.sub.3  CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 n.sub.D.sup.20 1.5945                    54  CH.sub.3                                                                         H  CH.sub.3  C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5984                    55  CH.sub.3                                                                         H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5845                    56  CH.sub.3                                                                         H  CH.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5776                    57  CH.sub.3                                                                         H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      5-Cl    0 n.sub.D.sup.20 1.5934                    58  CH.sub.3                                                                         H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.2 CH.sub.2 CH.sub.3                                                           5-Cl    0 n.sub.D.sup.20 1.5713                    59  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      --      1 n.sub.D.sup.20 1.5470                    60  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             5-Cl    1                                          61  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             5-Cl    1                                          62  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      5-Cl    1 n.sub.D.sup.20 1.5630                    63  H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      --      2                                          64  H  H  CH.sub.2 CH.sub. 3                                                                      C.sub.2 H.sub.5                                                                      --      2                                          65  H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      --      2                                          66  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             5-Cl    2                                          67  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             2-Cl    0 mp 60.5-65° C.                    68  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.3                                                                             2-Cl    0                                          69  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             2-Cl    0 mp 60-62° C.                      70  H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             2-Cl    0                                          71  H  H  CH.sub.3  CH.sub.3                                                                             2-Cl    0 mp 95.5-100° C.                   72  H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      2-Cl    0 mp 55-62° C.                      73  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      2-Cl    0 n.sub.D.sup.20 1.5983                    74  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                      2-Cl    0                                          75  H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      2-Cl    0 mp 49-56.5° C.                    76  H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      2-Cl    0                                          77  H  H  CH.sub.2 C CH                                                                           C.sub.2 H.sub.5                                                                      2-Cl    0                                          78  H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4-Cl    0 n.sub.D.sup.20 1.5909                    79  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-Cl    0 n.sub.D.sup.20 1.5917                    80  H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      4-Cl    0 n.sub.D.sup.20 1.5987                    81  H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      4-Cl    0 n.sub.D.sup.20 1.6002                    82  H  H  CH.sub.3  CH.sub.3                                                                             4-Cl    0 n.sub.D.sup.20 1.6112                    83  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-Cl    0 n.sub.D.sup.20 1.5960                    84  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-Cl    0 n.sub.D.sup.20 1.5855                    85  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-F     0 n.sub.D.sup.20 1.5793                    86  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-F     0 n.sub.D.sup.20 1.5751                    87  H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             4-F     0                                          88  H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4-F     0 n.sub.D.sup.20 1.5603                    89  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-F     0 n.sub. D.sup.20 1.5359                   90  H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      4-F     0 n.sub.D.sup.20 1.5810                    91  H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             2-F     0 n.sub.D.sup.20 1.5852                    92  H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.3                                                                             2-F     0                                          93  H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             2-F     0                                          94  H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             2-F     0                                          95  H  H  CH.sub.2 CCH                                                                            CH.sub.3                                                                             2-F     0                                          96  H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      2-F     0                                          97  H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      2-F     0                                          98  H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      2-F     0                                          99  H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      2-F     0                                          100 H  H  CH.sub.3  CH.sub.2 CH.sub.2 CH.sub.3                                                           2-F     0                                          101 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                           2-F     0                                          102 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CH.sub.2 CH.sub.3                                                           2-F     0                                          103 H  H  CH.sub.2 CHCHCl                                                                         CH.sub.2 CH.sub.2 CH.sub.3                                                           2-F     0                                          104 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-OCH.sub.3                                                                           0 n.sub.D.sup.20 1.5872                    105 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-OCH.sub.3                                                                           0 n.sub.D.sup.20 1.5902                    106 H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             4-OCH.sub.3                                                                           0                                          107 H  H  CH.sub.2 CCH                                                                            CH.sub.3                                                                             4-OCH.sub.3                                                                           0                                          108 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4-OCH.sub.3                                                                           0                                          109 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-OCH.sub.3                                                                           0 n.sub.D.sup.20 1.5818                    110 H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      4-OCH.sub.3                                                                           0 n.sub.D.sup.20 1.5841                    111 H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      4-OCH.sub.3                                                                           0                                          112 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             6-OCH.sub.3                                                                           0 n.sub.D.sup.20 1.5879                    113 H  H  CH.sub.3  CH.sub.2 CH.sub.3                                                                    6-OCH.sub.3                                                                           0 n.sub.D.sup.20 1.5827                    114 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                    6-OCH.sub.3                                                                           0 n.sub.D.sup.20 1.5842                    115 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub. 2 CH.sub.3                                                          6-OCH.sub.3                                                                           0                                          116 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-OCHF.sub.2                                                                          0                                          117 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-OCHF.sub.2                                                                          0                                          118 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-OCF.sub.3                                                                           0                                          119 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4-OCF.sub.3                                                                           0                                          120 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-OCF.sub.3                                                                           0                                          121 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-CF.sub.3                                                                            0                                          122 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             6-F     0                                          123 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      6-F     0                                          124 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-SCF.sub.3                                                                           0                                          125 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-SCF.sub.3                                                                           0                                          126 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             2-OCH.sub.3                                                                           0                                          127 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             2-OCHF.sub.2                                                                          0                                          128 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      2-OCHF.sub.2                                                                          0                                          129 H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             2-OCF.sub.3                                                                           0                                          130 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             2-CH.sub.3                                                                            0 Oily                                     131 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      2-CH.sub.3                                                                            0 n.sub.D.sup.20 1.5539                    132 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-CH.sub.3                                                                            0 n.sub.D.sup.20 1.5871                    133 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-CH.sub.3                                                                            0 n.sub.D.sup.20 1.5880                    134 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-CH.sub.3                                                                            0 n.sub.D.sup.20 1.5614                    135 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             6-CH.sub.3                                                                            0                                          136 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             6-CH.sub.3                                                                            0                                          137 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      6-CH.sub.3                                                                            0                                          138 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      6-CH.sub.3                                                                            0                                          139 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-CN    0                                          140 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-CN    0                                          141 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-CN    0                                          142 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-SCH.sub.3                                                                           0                                          143 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-SCH.sub.3                                                                           0                                          144 H  H  CH.sub.3  CH.sub.3                                                                             4-SCH.sub.3                                                                           0 mp 69-73°  C.                     145 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4-SCH.sub.3                                                                           0                                          146 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-SCH.sub.3                                                                           0 mp 53-60° C.                      147 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4,5-Cl.sub.2                                                                          0                                          148 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4,5-Cl.sub.2                                                                          0                                          149 H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             4,5-Cl.sub.2                                                                          0                                          150 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4,5-Cl.sub.2                                                                          0                                          151 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4,5-Cl.sub.2                                                                          0                                          152 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-F, 5-Cl                                                                             0 n.sub.D.sup.20 1.5878                    153 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-F, 5-Cl                                                                             0 mp 56.5-61° C.                    154 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4-F, 5-Cl                                                                             0 n.sub.D.sup.20 1.5299                    155 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-F, 5-Cl                                                                             0 n.sub.D.sup.20 1.5532                    156 H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      4-F, 5-Cl                                                                             0                                          157 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             2,4-F.sub.2                                                                           0                                          158 H  H  CH.sub.2 CH.sub. 3                                                                      C.sub.2 H.sub.5                                                                      2,4-F.sub.2                                                                           0                                          159 H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              CH.sub.3                                                                             4-F, 6-Cl                                                                             0                                          160 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-F, 6-Cl                                                                             0                                          161 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4,6-F.sub.2                                                                           0 n.sub.D.sup.20 1.5719                    162 H  H            CH.sub.3                                                                             4,6-F.sub.2                                                                           0                                          163 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4,6-F.sub.2                                                                           0                                          164 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      4,6-F.sub.2                                                                           0 n.sub.D.sup.20 1.5726                    165 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4,6-F.sub.2                                                                           0 n.sub.D.sup.20 1.5662                    166 H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                      4,6-F.sub.2                                                                           0                                          167 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4,5-F.sub.2                                                                           0                                          168 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4,5-F.sub.2                                        169 H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      5-CF.sub.3, 6-Cl                                                                      0                                          170 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-OCH.sub.3, 5-CF.sub.3                                                               0                                          171 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                           4-OCH.sub. 3, 5-CF.sub.3                                                              0                                          172 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             5-CF.sub.3, 6-OCH.sub.3                                                               0                                          173 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      2-OCH.sub.3, 5-CF.sub.3                                                               0                                          174 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-Cl, 5-CF.sub.3                                                                      0                                          175 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             4-OCF.sub.3, 5-CH.sub.3                                                               0                                          176 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      4-OCF.sub.3, 5-CH.sub.3                                                               0                                          177 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             2-OCH.sub.3, 5-CF.sub.3                                                               0                                          178 H  H  CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      2-OCH.sub.3, 5-CF.sub.3                                                               0                                          179 H  H                                                                                 ##STR12##                                                                              C.sub.2 H.sub.5                                                                      --      0                                          180 H  H  CH.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             2-CH.sub.3                                                                            0 mp 58-61° C.                      181 H  H  CH.sub.3  C.sub.2 H.sub.5                                                                      2-CH.sub.3                                                                            0 n.sub.D.sup.20 1.5822° C.         182 H  H  CH.sub.3  CH.sub.3                                                                             4-F, 5-Cl                                                                             0 mp 78-84° C.                      183 H  H  C.sub.2 H.sub.5                                                                         CH.sub.3                                                                             4-CF.sub.3                                                                            0 mp. 52-58° C.                     184 H  H  C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      4-CF.sub.3                                                                            0 mp. 48-56° C.                     185 H  H  C.sub.2 H.sub.5                                                                         CH.sub.3                                                                             4-OCF.sub.3                                                                           0                                          186 H  H  C.sub.2 H.sub.5                                                                         CH.sub.3                                                                             4-OCHF.sub.2                                                                          0                                          187 H  H  CH.sub.2 CHCH.sub.2                                                                     CH.sub.3                                                                             4-SCF.sub.3                                                                           0                                          188 H  H  CH.sub.2 CHCHCl                                                                         CH.sub.3                                                                             4-Cl    0 n.sub.D.sup.20 1.5870                    189 H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      4-Cl    0 n.sub.D.sup.20 1.6002                    190 H  H  CH.sub.2 CHCH.sub.2                                                                     C.sub.3 H.sub.7                                                                      4-Cl    0 n.sub.D.sup.20 1.5740                    191 H  H  CH.sub.2 CHCHCl                                                                         C.sub.3 H.sub.7                                                                      4-Cl    0 n.sub.D.sup.20 1.5886                    192 H  H  CH.sub.2 CHCHCl                                                                         C.sub.2 H.sub.5                                                                      2-CH.sub.3                                                                            0 n.sub.D.sup.20 1.5875                    __________________________________________________________________________

BACKGROUND EXAMPLES ##STR13##

5-[2-(3,4-dichlorophenylthio)ethyl]-3-propionyloxy-2-cyclohexenone (1.63g) and dimethylaminopyridine (0.45 g) were dissolved in acetonitrile (20ml), followed by one-hour heat-refluxing. After the completion of thereaction, the reaction product was poured into diluted hydrochloricacid, followed by extraction with ethyl acetate three times. The organicphase was dried over anhydrous sodium sulfate and the solvent wasremoved by evaporation under reduced pressure and then the residue waspurified through silicagel column chromatography(hexane:ethylacetate=85:15) to give5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-propionyl-2-cyclohexenone(1.44 g).

BIOTEST EXAMPLES ##STR14##

(Active compound disclosed by Japanese Patent Laid-open No. 115349/1979)##STR15##

(Active compound disclosed by Japanese Patent Laid-open No. 115349/1979)

Example 2

Herbicidal test by foliage application on upland field weeds (I)

Formulation of Active Compounds

Carrier: 5 parts by weight of acetone

Emulsifier: 1 part by weight of benzyloxy polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof each of the active compounds according to the present invention wasmixed with the stated amount of carrier and with the stated amount ofemulsifier, and the resulting emulsifiable concentrate was then dilutedwith water to the desired concentrations.

Test Procedures

In a greenhouse, a number of test pots each having an area of 1000 cm²were charged with soil taken from a cultivated field. Onto the soilsurfaces in the respective test pots were sown and grown the seeds ofbarnyard grass (Echinochloa crus-galli), fingergrass (Digitariaadscendens), goose grass (Eleusine indica), green foxtail (Setariaviridis), oat (Avena fatua L.) and dent foxtail (Alopeculus aequalis),respectively. When the respective weeds had grown to heights in therange of from 3 to 10 cm in the test pots, predetermined dosages of theactive compound formulation mentioned above were uniformly sprayed ontothe foliage of the test weeds in the respective test pots.

Four weeks after the application of the active compound formulations,the degree of damage to the weeds and the degree of the phytotoxicity onthe crop were determined based on the following assessment rate:

    ______________________________________                                        Assessment rate of herbicidal effect                                          10:  Herbicidal effect versus                                                                        100% (completely killed)                                    non-treated soil surface                                                 9:   Herbicidal effect versus                                                                         90% to less than 100%                                      non-treated soil surface                                                 8:   Herbicidal effect versus                                                                        from 80% to less than 90%                                   non-treated soil surface                                                 7:   Herbicidal effect versus                                                                        from 70% to less than 80%                                   non-treated soil surface                                                 6:   Herbicidal effect versus                                                                        from 60% to less than 70%                                   non-treated soil surface                                                 5:   Herbicidal effect versus                                                                        from 50% to less than 60%                                   non-treated soil surface                                                 4:   Herbicidal effect versus                                                                        from 40% to less then 50%                                   non-treated soil surface                                                 3:   Herbicidal effect versus                                                                        from 30% to less than 40%                                   non-treated soil surface                                                 2:   Herbicidal effect versus                                                                        from 20% to less than 30%                                   non-treated soil surface                                                 1:   Herbicidal effect versus                                                                        from 10% to less than 20%                                   non-treated soil surface                                                 0:   Herbicidal effect versus                                                                        less than 10%                                               non-treated soil surface                                                                        (no herbicidal effect)                                 Assessment rate of phytotoxicity                                              10:  Herbicidal effect versus                                                                        100% (completely killed                                     non-treated soil surface                                                                        fatal damage)                                          9:   Herbicidal effect versus                                                                         90% to less than 100%                                      non-treated soil surface                                                 8:   Herbicidal effect versus                                                                        from 80% to less than 90%                                   non-treated soil surface                                                 7:   Herbicidal effect versus                                                                        from 70% to less than 80%                                   non-treated soil surface                                                 6:   Herbicidal effect versus                                                                        from 60% to less than 70%                                   non-treated soil surface                                                 5:   Herbicidal effect versus                                                                        from 50% to less than 60%                                   non-treated soil surface                                                 4:   Herbicidal effect versus                                                                        from 40% to less than 50%                                   non-treated soil surface                                                 3:   Herbicidal effect versus                                                                        from 30% to less than 40%                                   non-treated soil surface                                                 2:   Herbicidal effect versus                                                                        from 20% to less than 30%                                   non-treated soil surface                                                 1:   Herbicidal effect versus                                                                        from 10% to less than 20%                                   non-treated soil surface                                                 0:   Herbicidal effect versus                                                                        less than 10%                                               non-treated soil surface                                                                        (no phytotoxicity)                                     ______________________________________                                    

The test results are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Active                                                                              Dosage of active                                                        compound                                                                            compound Barnyard                                                                           Finger                                                                            Goose                                                                             Green  Dent                                       No.   g/ha     grass                                                                              grass                                                                             grass                                                                             foxtail                                                                           Oat                                                                              foxtail                                    __________________________________________________________________________     2    500      10   10  10  10  10 --                                          3    500      10   10  10  10  10 --                                          5    500      10   10  10  10  10 10                                         21    500      10    9   9   9  10 10                                         37    500      10   10  10  10  10 10                                         67    500      10   10  10  10   9 --                                         69    500      10   10  10  10   9 --                                         83    500      10   10  10  10  10 10                                         89    500      10   10  10  10  10 --                                         114   500      10    8   9   7   9 --                                         131   500      10   10  10  10  10 --                                         __________________________________________________________________________

Example 3

Post-emergence foliage treatment on upland field weeds

In a greenhouse, a number of test pots each having an area of 2000 cm²were charged with soil taken from a cultivated field. Seeds of soy beanwere sown onto the soil surfaces in the respective test pots. Each ofthe thus sown soil surfaces was covered with a soil layer to a height of1 cm. Into the soil of the respective soil layers in the respective testpots had beforehand been mixed the seeds of barnyard grass, fingergrass, goose grass, green foxtail, causeway grass (Poa annua) andBermuda grass (Cynodon dactylon), respectively.

Ten days after the seed-sowing and soil-covering when the weeds enteredthe second leaf stage on average while the soy beans entered the earlyleafing stage of true leaves, predetermined dosages of the activecompound formulations prepared as in Example 2 mentioned above wereuniformly sprayed onto the foliage of the test plants in the respectivetest pots.

Three weeks after the spraying of the active compound formulations, thedegree of the herbicidal effect on the weeds and the degree of thephytotoxicity on the crop were determined in a similar manner as inExample 2, the results of which are shown in Table 3:

                                      TABLE 3                                     __________________________________________________________________________            Dosage of active                                                                       Herbicidal effect on weeds  Phytotoxic                               compound Barnyard                                                                           Finger                                                                            Goose                                                                             Green                                                                             Causeway                                                                            Bermuda                                                                            effect on                                g/ha     grass                                                                              grass                                                                             grass                                                                             foxtail                                                                           grass grass                                                                              soybeans                         __________________________________________________________________________    Active                                                                        compound No.                                                                   3      500      10   10  10  10  10    10   2                                        200      10   10  10  10  9     10   1                                        100       9    9   9   9  9      9   0                                 37     500      10   10  10  10  10    10   2                                        200      10   10  10  10  8     10   1                                        100       9    9   9   9  7     10   0                                 67     500      10   10  10  10  9     10   1                                        200      10   10  10  10  7     10   0                                        100       9    9   9   8  6      9   0                                 83     500      10   10  10  10  9     10   1                                        200      10   10  10  10  9     10   0                                        100       9    7   9   9  7      9   0                                 89     500      10   10  10  10  6     10   0                                        200      10   10  10  10  1     10   0                                        100       9    9  10   9  0     10   0                                131     500      10   10  10  10  9     10   0                                        200      10   10  10  10  9     10   0                                        100       9    7   9   9  7      9   0                                184     500      10   10  10  10  10    10   2                                        200      10   10  10  10  9     10   1                                        100      10    9  10  10  9      9   0                                Comparative                                                                   C-1     500      10   10  10  10  4     10   1                                        200       8    4   8   8  1      9   0                                C-2     500      10   10   9   7  2     10   0                                        200       9    7   5   4  0      8   0                                __________________________________________________________________________

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A 3-hydroxy-2-cyclohexen-1-one of the formula##STR16## wherein R¹ and R² each is hydrogen or methyl,R³ is C₁₋₄ alkyl,cyclopropylmethyl, C₃₋₄ alkenyl which may be substituted by one to threehalogen atoms or C₃₋₄ alkynyl, R⁴ is C₁₋₄ alkyl, R⁵ each independentlyis halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy,C₁₋₄ alkylthio, C₁₋₄ haloalkylthio or cyano, n is 0, 1 or 2, and m is 0,1 or
 2. 2. A compound according to claim 1, whereinR¹ and R² each ishydrogen or methyl, R³ is C₁₋₄ alkyl or C₃₋₄ alkenyl which may besubstituted by one to three halogen atoms, R⁴ is C₁₋₃ alkyl, R⁵ eachindependently is chlorine, fluorine or trifluoromethyl, n is 0, 1 or 2,and m is 0, 1 or
 2. 3. A compound according to claim 1, whereinR¹ and R²each is hydrogen, R³ is ethyl or allyl, R⁴ is methyl or ethyl, R⁵ ischlorine, fluorine or trifluoromethyl, n is 0, and m is 0 or
 1. 4. Acompound according to claim 1, wherein such compound is5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-oneof the formula ##STR17##
 5. A compound according to claim 1, whereinsuch compound is5-[2-(3-chlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-oneof the formula ##STR18##
 6. A compound according to claim 1, whereinsuch compoundis5-[2-(3-chloro-4-fluorophenylthio-ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-oneof the formula ##STR19##
 7. A compound according to claim 1, whereinsuch compound is5-{2-[3-chloro-4-trifluoromethyl)-phenylthio]ethyl}-3-hydroxy-2-(1-ethoxyimino)ethyl-2-cyclohexen-1-oneof the formula ##STR20##
 8. A compound according to claim 1, wheriensuch compound is5-[2-(3-chloro-2-methylphenylthio)ethyl]-3-hydroxy-2-(1-allyloxyimino)propyl-2-cyclohexen-1-oneof the formula ##STR21##
 9. A compound according to claim 1, whereinsuch compound is5-[2-(3-chloro-4-fluorophenylthio)ethyl]-3-hydroxy-2-(1-allyloxyimino)propyl-2-cyclohexen-1-oneof the formula ##STR22##
 10. A compound according to claim 1, whereinsuch compound is5-[2-(2-methyl-3-chloro-phenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-oneof the formula ##STR23##
 11. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim 1 and adiluent.
 12. A method of combating unwanted vegetation which comprisesapplying to such vegetation or to a locus from which it is desired toexclude such vegetation a herbicidally effective amount of a compoundaccording to claim
 1. 13. The method according to claim 12, wherein suchcompoundis5-[2-(3,4-dichlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-one,5-[2-(3-chlorophenylthio)ethyl]-3-hydroxy-2-(1-ethoxyimino)propyl-2-cyclohexen-1-one,5-[2-(3-chloro-4-fluorophenylthio)ethyl]-3-hydroxy-2-(1-methoxyimino)propyl-2-cyclohexen-1-one,5-{2-[3-chloro-4-(trifluoromethyl)-phenylthio]ethyl}-3-hydroxy-2-(1-ethoxyimino)ethyl-2-cyclohexen-1-one,5-[2-(3-chloro-2-methylphenylthio)ethyl]-3-hydroxy-2-(1-allyloxyimino)propyl-2-cyclohexen-1-one,5-[2-(3-chloro-4-fluorophenylthio)ethyl]-3-hydroxy-2-(1-allyloxyimino)propyl-2-cyclohexen-1-oneor5-{2-(2-methyl-3-chloro-phenylthio)ethyl}-3-hydroxy-2-(1-ethoxyimino)propyl-2-clclohexen-1-one.